Calorimetric study of the glassy state. XV. Thermodynamic study of pinacol hexahydrate and pinacol-d2 hexadeuterate.
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概要
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The heat capacities of pinacol hexahydrate and its deuterate analogue were measured in the temperature region between 13 and 260 K. A phase transition was found and the temperature of transition was determined to be 192.14 K for the hydrate and 191.17 K for the deuterate, respectively. The enthalpy and entropy of the transition were estimated to be 924 J mol<SUP>−1</SUP> and 5.10 J K<SUP>−1</SUP> mol<SUP>−1</SUP> for the hydrate and 944 J mol<SUP>−1</SUP> and 5.28 J K<SUP>−1</SUP> mol<SUP>−1</SUP> for the deuterate. The transition was interpreted as the order-disorder change of the orientations of the pinacol molecule. Besides the phase transitions, an additional anomaly was found around 150 K for the hydrate and two around 130 K and around 160 K for the deuterate, respectively. All of them are relaxational in their characteristics and interpreted as glass transitions due to freezing of reorientational motions of the water molecule and the pinacol molecule. The transition temperature and the activation enthalpy for the higher glass transition of the deuterate were estimated to be 167.2 K and (34±4) kJ mol<SUP>−1</SUP>, respectively.
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著者
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Seki Syuzo
Department Of Chemistry Faculity Of Science Osaka University
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Suga Hiroshi
Department Of Chemistry Faculty Of Science Osaka University
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MATSUO Takasuke
Department of Chemistry and Microcalorimetry Research Center, Faculty of Science, Osaka University
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Oguni Masaharu
Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University
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Matsuo Takasuke
Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University
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Suga Hiroshi
Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University
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